Edward c



I Patented Nov. 22, 1932 UNITED STATES PATENT OFFICE EDWARD C. HOLTON, OF OLMSTED FALLS, OHIO, ASSIGNOR TO THE SHEBWIN-WILLIAMS COMPANY, OF CLEVELAND, OHIO, A CORPORATION OF OHIO IBASll? FOB PAINTS, VABNISHES, AND LACQUERS, AND METHOD OI MAKING THE SAME No Drawing.

This invention relates to a destructively distilled, mixed glyceride condensation product, and process of making the same, for use I as a base for paint, varnish or lacquer.

.5 The present invention relates to certain improvements in the product and process disclosed in my prior Patent No. 1,7 99,420, granted April 7, 1931, and has for its object a product that will be more water-resistant and possess a somewhat better gloss than the product resulting from the process disclosed in said patent.

A further object of the invention is to utilize the so-called drying oils in the manuv facture of paint and varnish bases by a process that will avoid some of the objections to such oils. For example, when China-wood oil is heated to a temperature of about 260 C. it has a tendency to rapidly gelatinize and it requires great skill and very speedy action on the part of the operator to save the batch when this condition arises. A very ra id introduction of rosin or cold stand-oil to 0 ill the batch below 200 C. ma succeed in saving it from complete destructlon but, if the operator fails to add the rosin or cold stand-oil quickly enough, the batch becomes a rubbery, vesiculated, insoluble, worthless mass and may even ignite" and cause a disastrous confiagration; v

Linseed oil and perilla oil may be heated to these high temperatures with much less risk yet care must always be taken that the critical temperature is not exceeded, since,

if this happens, the reaction becomes exothermic, and very rapid decomposition ensues.

It is one of the objects of the present invention to provide a method of utilizing these drying oils that will obviate the above mentioned difficulties. v 1

In my prior Patent No. 1,779,420, I have described and claimed a condensation product made from castor oil and other materials by a process of partial destructive distillation. I have discovered that a mixture of Application filed February 24, 1931. Serial No. 518,038.

castor oil and the well-known drying oils, such as linseed, China-wood, and perilla oil, when subjected to partial destructive distillation, produces a base material which has some advantages over the product obtained by a partial destructive distillation of the castor oil alone, as described in myaforesaid patent.

When China-wood oil is substituted, in part, for castor oil, the final product made, when used in protective coating, is found to dry somewhat harder and will be more waterresistant than the product made from castor oil as disclosed in the patent. When linseed oil and perilla oil are used in partial substitution for the castor oil, the final products which are obtained have somewhat better drying properties than the productfrom castor oil alone and they also possess a somewhat better gloss, although the resistance 85 to water is inferior to that of the product produced from a mixture of castor oil and China-wood oil.

' In practicinglthe present invention, I may use 500 parts, by weight, of castor oil and -500 parts of any of the drying oils referred to above. These oils are mixed 'together and destructively distilled until the residue of polymeric esters is approximately 85 per cent of the original mixture. In this 7 operation the castor oil, in the mixture, will lose about 26 per cent of its weight and the drying oil will lose from 3 to 5 per cent of its weight. The retort is then cooled to a temperature below 290 C. and 800 arts of glycerine are gradually introduce The mixture is then heated for a short time at temperatures well above the boiling point of water but below the boiling point of, lycerine, and then 1200 parts of phthalic an ydrid are gradually added, the temperature being maintained about mid-way between the boiling point of phthalic anhydrid and that of water. When the reaction has proceeded to the optimum degree, which is indicated by the first appearance of clarity and homogeneity in place of turbidity and heterogeneity, the mixture is run into cooling pans to cool or into mixing tanks to be thinned with the proper solvent mixtures which vary some what according to the use to which the product is to be put.

By varying the proportions of polymeric esters of undecylenic acid, glycerine and phthalic acid anhydride the physical properties of the resulting compounds are varied. While, in the example given, the distillation is stopped when the residue is approximately 85 per cent of the original mixture, this procedure may be varied so that the residue will be from 70 to 90 per cent of the original mixture, and the amount of glycerine that is added may vary from one-half to three times the weight of said residue. The amount of undecylenic esters that are added may vary from three-fourths to five times the weight of the material to which they are added. A

I lessening of undecylenic esters ives a harder product while an increase 0 undecylenic esters produces a softer compound.

Also by the use of other polyhydric alcohols and other polybasic acids along with the esters of undecylenic acid and its polymers pgoducts of-harderor softer consistency may obtained. In the specific example given, the distillation of the mixture of castor oil and a drying oil is carried on until. the distillate is about 15 per cent ofrthe original mixture and the polymeric esters are about 85 per cent of the weight of the original mixture. I do not wish to limit myself to these proportions since the distillation may be carried much further and still yield a usable product. However, since there is a tendency or these undecylenic compounds to discolor as the distillation progresses, I usually prefer to stop the distillation within a range of 10 to per cent of distillate, especially when the distillation is carried on at atmosheric pressures.- There are some advanta es m the use of reduced pressures during istillation especially if, a light colored product is desired; and, under these conditions, I prefer to use some commercial form of vacuum pump with suitable condenser for the recovery of the valuable distillate.

In the specific example given, the order of procedure is to esterify with lycerine before condensing with phthalic an ydride. This is the wish to limit myself to this order of procedure since. by the exercise of care it is possible to obtain a usable product if the phthalic acid anhydride is added before the glyoerine or simultaneously with the glycerme.

As above stated, I prefer to use, as the base material, a mixture of castor oil with lip; seed oil, China-wood oil, or perilla 011,

referable method but I do not these are the principal vegetable dryingoils of commerce. Instead of using a mixture of castor oil and one of these vegetable drying oils, it is possible to use a mixture of the eastor oil with a combination of two or more of these vegetable drying oils. It would be possible to also use, in place of the three vegetable drying oils mentioned, some of the scarcer vegetable drying oils but, ordinarily, commercial considerations and the element of cost would lead to the use of one or more of the three vegetable drying oils mentioned. However, I have found that the best results are obtained by the use of a vegetable drying oil havin an iodine value of 160 or above and this cIassification would include the three ve etable drying oils s ecifically mentioned.

I-Iaving thus descri ed my invention, I claim: p

1. The steps of the hereindescribed method which consist in destructively distillin a mixture of castor oil and a vegetable drying oil having an iodine value above ,160 untl' the residue is from sevent to ninety per cent of the original weight 0 said mixture, and then heating such residue with a polyhydric alcohol.

2. The steps of the hereindescribed method which consist in destructively distilling a mixture of castor oil and a vegetabledrymig oil having an iodine value above 160 unt the residue is from seventy to ninety per cent of the original weight of said mixture,

then heating such residue with a polyhydric alcohol, with'addition of a member selectedfrom the group consisting of organic polybasic'acids or acid anhydrides until condensationtakes place andthe mass becomes homogeneous, clear and substantially tran' uil.

3. The steps of the hereindescribed met 0d which consist in destructively distilling a mixture of castor oil and a vegetable drym oil having an iodine value above 160 unti the residue is from sevent to ninety per cent of the original weight 0 said mixture and then heatingsuch residue with the addition of glq cerine and phthalic anhydride.

4. he steps ofthe hereindescribedmethod which consist in destructively distilling a.

mixture of castor oil and a vegetable drying oil having an iodine value above 160 until the residue is from sevent to ninety per cent of the original weight 0 said mixture, and then heating such residue with the addition of one-half to three times its weight of glycerine the esterifiable constituents of the residue are substantially esterified.

5. The steps ofthe hereindescribed method which consist in. destructively distilling a mixture of castor oil and a vegetable drying oil having an iodine value above 160 until the residue is from seventy to ninety per cent of the original weight of said mixture, then heating such residue with the addition of {me-half to three times its weight of glycerine until the esterifiable constituents of the residue are substantial! esterified, and then heatin the product us obtained with from threeourths to five times its weight of phthalic anhydride until condensation takes place and the mass becomes homogeneous, clear and substantially tranquil. Y

6. The material produced by' the method defined in claim 2. Y 10 7. The material. produced by the method defined in claim 5.

In testimony whereof, I hereunto afix my signature. I

EDWARD HOLTON. 

